Experimental and computational studies of Criegee Intermediate Reactions with NH3 and CH3NH2

Rabi Chhantyal Pun; Robin Shannon; David Tew; Rebecca L. Caravan; Marta Duchi; Callum Wong; Aidan Ingham; Charlotte Feldman; Max McGillen; Anwar Khan; Ivan O Antonov; Brandon Rotavera; Krupa Ramasesha; David Osborn; CA Taatjes; A Percival; Dudley Shallcross; Andrew Orr-Ewing

doi:10.1039/C8CP06810K

Experimental and computational studies of Criegee Intermediate Reactions with NH₃ and CH₃NH₂

Rabi Chhantyal Pun, Robin Shannon, David Tew, Rebecca L. Caravan, Marta Duchi, Callum Wong, Aidan Ingham, Charlotte Feldman, Max McGillen, Anwar Khan, Ivan O Antonov, Brandon Rotavera, Krupa Ramasesha, David Osborn, CA Taatjes, A Percival, Dudley Shallcross, Andrew Orr-Ewing

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Abstract

Ammonia and amines are emitted into the troposphere by various natural and anthropogenic sources, where they have a significant role in aerosol formation. Here, we explore the significance of their removal by reaction with Criegee intermediates, which are produced in the troposphere by ozonolysis of alkenes. Rate coefficients for the reactions of two representative Criegee intermediates, formaldehyde oxide (CH₂OO) and acetone oxide ((CH₃)₂COO) with NH₃ and CH₃NH₂ were measured using cavity ring-down spectroscopy. Temperature-dependent rate coefficients, k (CH₂OO + NH₃) = (3.1 ± 0.5) x 10^-20 T² exp (1011 ± 48 / T) cm³ s^-1 and k (CH₂OO + CH₃NH₂) = (5 ± 2) x 10^-19 T² exp (1384 ± 96 / T) cm³ s^-1 were obtained in the 240 to 320 K range. Both the reactions of CH₂OO were found to be independent of pressure in the 10 to 100 Torr (N₂) range, and average rate coefficients k (CH₂OO + NH₃) = (8.4 ± 1.2) x 10^-14 cm³ s^-1 and k (CH₂OO + CH₃NH₂) = (5.6 ± 0.4) x 10^-12 cm³ s^-1 were deduced at 293 K. An upper limit of ≤ 2.7 x 10^-15 cm³ s^-1 was estimated for the rate coefficient of the (CH₃)₂COO + NH₃ reaction. Complementary measurements were performed with mass spectrometry using synchrotron radiation photoionization giving k (CH₂OO + CH₃NH₂) = (4.3 ± 0.5) x 10^-12 cm³ s^-1 at 298 K and 4 Torr (He). Photoionization mass spectra indicated production of NH₂CH₂OOH and CH₃N(H)CH₂OOH functionalized organic hydroperoxide adducts from CH₂OO + NH₃ and CH₂OO + CH₃NH₂ reactions, respectively. Ab initio calculations performed at the CCSD(T)(F12*)/cc-pVQZ-F12//CCSD(T)(F12*)/cc-pVDZ-F12 level of theory predicted pre-reactive complex formation, consistent with previous studies. Master equation simulations of the experimental data using the ab initio computed structures identified submerged barrier heights of -1.9 ± 0.1 kJ mol^-1 and -22.4 ± 0.2 kJ mol^-1 for the CH₂OO + NH₃ and CH₂OO + CH₃NH₂ reactions, respectively. The reactions of NH₃ and CH₃NH₂ with CH₂OO are not expected to compete with its removal by reaction with (H₂O)₂ in the troposphere. Similarly, losses of NH₃ and CH₃NH₂ by reaction with Criegee intermediates will be insignificant compared with reactions with OH radicals.

Original language	English
Pages (from-to)	14042-14052
Number of pages	11
Journal	Physical Chemistry Chemical Physics
Volume	21
Issue number	26
Early online date	8 Jan 2019
DOIs	https://doi.org/10.1039/C8CP06810K
Publication status	Published - 3 Jul 2019

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Kinetic Studies of Reactive Intermediates from the Oxidation of Atmospheric Alkenes
Orr-Ewing, A. J. (Principal Investigator)
1/04/17 → 30/09/20
Project: Research
HOMER: Fellowship - Max McGillen
Shallcross, D. E. (Principal Investigator)
4/04/16 → 3/04/18
Project: Research
Gas phase studies of the kinetics of Criegee Intermediates
Shallcross, D. E. (Principal Investigator) & Orr-Ewing, A. J. (Co-Principal Investigator)
30/06/13 → 31/12/16
Project: Research

Reaction Kinetics of Criegee Intermediates with Ammonia and Methylamine
Orr-Ewing, A. J. (Creator) & Pun, R. C. (Creator), University of Bristol, 29 Oct 2018
DOI: 10.5523/bris.3lfkl8guhfjf2ain57w18p7ue, http://data.bris.ac.uk/data/dataset/3lfkl8guhfjf2ain57w18p7ue
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Research Data Storage Facility (RDSF)
Alam, S. R. (Manager), Williams, D. A. G. (Manager) & Eccleston, P. E. (Manager)
IT Services
Facility/equipment: Facility
Various Computer Clusters, Storage Facility
University of Bristol
Facility/equipment: Equipment

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Chhantyal Pun, R., Shannon, R., Tew, D., Caravan, R. L., Duchi, M., Wong, C., Ingham, A., Feldman, C., McGillen, M., Khan, A., Antonov, I. O., Rotavera, B., Ramasesha, K., Osborn, D., Taatjes, CA., Percival, A., Shallcross, D., & Orr-Ewing, A. (2019). Experimental and computational studies of Criegee Intermediate Reactions with NH₃ and CH₃NH₂. Physical Chemistry Chemical Physics, 21(26), 14042-14052. https://doi.org/10.1039/C8CP06810K

@article{f25dd71721ac4337a91bcc8256fe37d2,

title = "Experimental and computational studies of Criegee Intermediate Reactions with NH3 and CH3NH2",

abstract = "Ammonia and amines are emitted into the troposphere by various natural and anthropogenic sources, where they have a significant role in aerosol formation. Here, we explore the significance of their removal by reaction with Criegee intermediates, which are produced in the troposphere by ozonolysis of alkenes. Rate coefficients for the reactions of two representative Criegee intermediates, formaldehyde oxide (CH2OO) and acetone oxide ((CH3)2COO) with NH3 and CH3NH2 were measured using cavity ring-down spectroscopy. Temperature-dependent rate coefficients, k (CH2OO + NH3) = (3.1 ± 0.5) x 10-20 T2 exp (1011 ± 48 / T) cm3 s-1 and k (CH2OO + CH3NH2) = (5 ± 2) x 10-19 T2 exp (1384 ± 96 / T) cm3 s-1 were obtained in the 240 to 320 K range. Both the reactions of CH2OO were found to be independent of pressure in the 10 to 100 Torr (N2) range, and average rate coefficients k (CH2OO + NH3) = (8.4 ± 1.2) x 10-14 cm3 s-1 and k (CH2OO + CH3NH2) = (5.6 ± 0.4) x 10-12 cm3 s-1 were deduced at 293 K. An upper limit of ≤ 2.7 x 10-15 cm3 s-1 was estimated for the rate coefficient of the (CH3)2COO + NH3 reaction. Complementary measurements were performed with mass spectrometry using synchrotron radiation photoionization giving k (CH2OO + CH3NH2) = (4.3 ± 0.5) x 10-12 cm3 s-1 at 298 K and 4 Torr (He). Photoionization mass spectra indicated production of NH2CH2OOH and CH3N(H)CH2OOH functionalized organic hydroperoxide adducts from CH2OO + NH3 and CH2OO + CH3NH2 reactions, respectively. Ab initio calculations performed at the CCSD(T)(F12*)/cc-pVQZ-F12//CCSD(T)(F12*)/cc-pVDZ-F12 level of theory predicted pre-reactive complex formation, consistent with previous studies. Master equation simulations of the experimental data using the ab initio computed structures identified submerged barrier heights of -1.9 ± 0.1 kJ mol-1 and -22.4 ± 0.2 kJ mol-1 for the CH2OO + NH3 and CH2OO + CH3NH2 reactions, respectively. The reactions of NH3 and CH3NH2 with CH2OO are not expected to compete with its removal by reaction with (H2O)2 in the troposphere. Similarly, losses of NH3 and CH3NH2 by reaction with Criegee intermediates will be insignificant compared with reactions with OH radicals. ",

author = "{Chhantyal Pun}, Rabi and Robin Shannon and David Tew and Caravan, {Rebecca L.} and Marta Duchi and Callum Wong and Aidan Ingham and Charlotte Feldman and Max McGillen and Anwar Khan and Antonov, {Ivan O} and Brandon Rotavera and Krupa Ramasesha and David Osborn and CA Taatjes and A Percival and Dudley Shallcross and Andrew Orr-Ewing",

year = "2019",

month = jul,

day = "3",

doi = "10.1039/C8CP06810K",

language = "English",

volume = "21",

pages = "14042--14052",

journal = "Physical Chemistry Chemical Physics",

issn = "1463-9076",

publisher = "Royal Society of Chemistry",

number = "26",

}

Chhantyal Pun, R, Shannon, R, Tew, D, Caravan, RL, Duchi, M, Wong, C, Ingham, A, Feldman, C, McGillen, M, Khan, A, Antonov, IO, Rotavera, B, Ramasesha, K, Osborn, D, Taatjes, CA, Percival, A, Shallcross, D & Orr-Ewing, A 2019, 'Experimental and computational studies of Criegee Intermediate Reactions with NH₃ and CH₃NH₂', Physical Chemistry Chemical Physics, vol. 21, no. 26, pp. 14042-14052. https://doi.org/10.1039/C8CP06810K

TY - JOUR

T1 - Experimental and computational studies of Criegee Intermediate Reactions with NH3 and CH3NH2

AU - Chhantyal Pun, Rabi

AU - Shannon, Robin

AU - Tew, David

AU - Caravan, Rebecca L.

AU - Duchi, Marta

AU - Wong, Callum

AU - Ingham, Aidan

AU - Feldman, Charlotte

AU - McGillen, Max

AU - Khan, Anwar

AU - Antonov, Ivan O

AU - Rotavera, Brandon

AU - Ramasesha, Krupa

AU - Osborn, David

AU - Taatjes, CA

AU - Percival, A

AU - Shallcross, Dudley

AU - Orr-Ewing, Andrew

PY - 2019/7/3

Y1 - 2019/7/3

N2 - Ammonia and amines are emitted into the troposphere by various natural and anthropogenic sources, where they have a significant role in aerosol formation. Here, we explore the significance of their removal by reaction with Criegee intermediates, which are produced in the troposphere by ozonolysis of alkenes. Rate coefficients for the reactions of two representative Criegee intermediates, formaldehyde oxide (CH2OO) and acetone oxide ((CH3)2COO) with NH3 and CH3NH2 were measured using cavity ring-down spectroscopy. Temperature-dependent rate coefficients, k (CH2OO + NH3) = (3.1 ± 0.5) x 10-20 T2 exp (1011 ± 48 / T) cm3 s-1 and k (CH2OO + CH3NH2) = (5 ± 2) x 10-19 T2 exp (1384 ± 96 / T) cm3 s-1 were obtained in the 240 to 320 K range. Both the reactions of CH2OO were found to be independent of pressure in the 10 to 100 Torr (N2) range, and average rate coefficients k (CH2OO + NH3) = (8.4 ± 1.2) x 10-14 cm3 s-1 and k (CH2OO + CH3NH2) = (5.6 ± 0.4) x 10-12 cm3 s-1 were deduced at 293 K. An upper limit of ≤ 2.7 x 10-15 cm3 s-1 was estimated for the rate coefficient of the (CH3)2COO + NH3 reaction. Complementary measurements were performed with mass spectrometry using synchrotron radiation photoionization giving k (CH2OO + CH3NH2) = (4.3 ± 0.5) x 10-12 cm3 s-1 at 298 K and 4 Torr (He). Photoionization mass spectra indicated production of NH2CH2OOH and CH3N(H)CH2OOH functionalized organic hydroperoxide adducts from CH2OO + NH3 and CH2OO + CH3NH2 reactions, respectively. Ab initio calculations performed at the CCSD(T)(F12*)/cc-pVQZ-F12//CCSD(T)(F12*)/cc-pVDZ-F12 level of theory predicted pre-reactive complex formation, consistent with previous studies. Master equation simulations of the experimental data using the ab initio computed structures identified submerged barrier heights of -1.9 ± 0.1 kJ mol-1 and -22.4 ± 0.2 kJ mol-1 for the CH2OO + NH3 and CH2OO + CH3NH2 reactions, respectively. The reactions of NH3 and CH3NH2 with CH2OO are not expected to compete with its removal by reaction with (H2O)2 in the troposphere. Similarly, losses of NH3 and CH3NH2 by reaction with Criegee intermediates will be insignificant compared with reactions with OH radicals.

AB - Ammonia and amines are emitted into the troposphere by various natural and anthropogenic sources, where they have a significant role in aerosol formation. Here, we explore the significance of their removal by reaction with Criegee intermediates, which are produced in the troposphere by ozonolysis of alkenes. Rate coefficients for the reactions of two representative Criegee intermediates, formaldehyde oxide (CH2OO) and acetone oxide ((CH3)2COO) with NH3 and CH3NH2 were measured using cavity ring-down spectroscopy. Temperature-dependent rate coefficients, k (CH2OO + NH3) = (3.1 ± 0.5) x 10-20 T2 exp (1011 ± 48 / T) cm3 s-1 and k (CH2OO + CH3NH2) = (5 ± 2) x 10-19 T2 exp (1384 ± 96 / T) cm3 s-1 were obtained in the 240 to 320 K range. Both the reactions of CH2OO were found to be independent of pressure in the 10 to 100 Torr (N2) range, and average rate coefficients k (CH2OO + NH3) = (8.4 ± 1.2) x 10-14 cm3 s-1 and k (CH2OO + CH3NH2) = (5.6 ± 0.4) x 10-12 cm3 s-1 were deduced at 293 K. An upper limit of ≤ 2.7 x 10-15 cm3 s-1 was estimated for the rate coefficient of the (CH3)2COO + NH3 reaction. Complementary measurements were performed with mass spectrometry using synchrotron radiation photoionization giving k (CH2OO + CH3NH2) = (4.3 ± 0.5) x 10-12 cm3 s-1 at 298 K and 4 Torr (He). Photoionization mass spectra indicated production of NH2CH2OOH and CH3N(H)CH2OOH functionalized organic hydroperoxide adducts from CH2OO + NH3 and CH2OO + CH3NH2 reactions, respectively. Ab initio calculations performed at the CCSD(T)(F12*)/cc-pVQZ-F12//CCSD(T)(F12*)/cc-pVDZ-F12 level of theory predicted pre-reactive complex formation, consistent with previous studies. Master equation simulations of the experimental data using the ab initio computed structures identified submerged barrier heights of -1.9 ± 0.1 kJ mol-1 and -22.4 ± 0.2 kJ mol-1 for the CH2OO + NH3 and CH2OO + CH3NH2 reactions, respectively. The reactions of NH3 and CH3NH2 with CH2OO are not expected to compete with its removal by reaction with (H2O)2 in the troposphere. Similarly, losses of NH3 and CH3NH2 by reaction with Criegee intermediates will be insignificant compared with reactions with OH radicals.

U2 - 10.1039/C8CP06810K

DO - 10.1039/C8CP06810K

M3 - Article (Academic Journal)

SN - 1463-9076

VL - 21

SP - 14042

EP - 14052

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

IS - 26

ER -

Experimental and computational studies of Criegee Intermediate Reactions with NH3 and CH3NH2

Abstract

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Projects

Kinetic Studies of Reactive Intermediates from the Oxidation of Atmospheric Alkenes

HOMER: Fellowship - Max McGillen

Gas phase studies of the kinetics of Criegee Intermediates

Datasets

Reaction Kinetics of Criegee Intermediates with Ammonia and Methylamine

Equipment

Research Data Storage Facility (RDSF)

Various Computer Clusters, Storage Facility

Cite this

Experimental and computational studies of Criegee Intermediate Reactions with NH₃ and CH₃NH₂